JP2011253980A - Organic electroluminescent element, organic electroluminescent element material, display device, and lighting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic EL element for which an organic EL material having light-emission with short wave, high light-emission efficiency, and long light-emission lifetime is used.SOLUTION: An organic EL element has a light-emitting layer that includes a compound represented by the following general formula (1).

Description

  The present invention relates to an organic electroluminescence element, an organic electroluminescence element material, a display device, and a lighting device.

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).

  Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them. The device emits light by utilizing the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving and portability.

  However, in organic EL elements for practical use in the future, development of organic EL elements that emit light efficiently and with high luminance with lower power consumption is desired.

  In Japanese Patent No. 3093796, a small amount of a phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to achieve an improvement in light emission luminance and a longer device lifetime.

  Further, an element having an organic light-emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped thereto (for example, JP-A 63-264692), and an 8-hydroxyquinoline aluminum complex is used as a host compound. For example, an element having an organic light emitting layer doped with a quinacridone dye (for example, JP-A-3-255190) is known.

  As described above, when light emission from excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, and thus the generation probability of luminescent excited species is 25%. Since the efficiency is about 20%, the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, since Princeton University reported on an organic EL device using phosphorescence emission from an excited triplet (MA Baldo et al., Nature, 395, 151-154 (1998)), Research on materials that exhibit phosphorescence has become active.

  For example, M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), US Pat. No. 6,097,147, and the like.

  When the excited triplet is used, the upper limit of the internal quantum efficiency is 100%. In principle, the luminous efficiency is four times that of the excited singlet, and there is a possibility that almost the same performance as a cold cathode tube can be obtained. Therefore, it is attracting attention as a lighting application.

  For example, S.M. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), etc., many compounds are being studied for synthesis centering on heavy metal complexes such as iridium complexes.

  In addition, the aforementioned M.I. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), studies have been made using tris (2-phenylpyridine) iridium as a dopant.

In addition, M.M. E. Thompson et al. In The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) used L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac), e 0 g, Tetsuo Tsutsui, etc., again The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), the dopant as tris (2-(p-tolyl) pyridine) iridium (Ir _{(ptpy) 3),} tris ( Studies using benzo [h] quinoline) iridium (Ir (bzq) ₃ ) and the like are being conducted (note that these metal complexes are generally called ortho-metalated iridium complexes).

  In addition, the S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001) and Japanese Patent Application Laid-Open No. 2001-247859, etc., attempts have been made to form devices using various iridium complexes.

  In order to obtain high luminous efficiency, in the 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. In addition, M.M. E. Thompson et al. Use various electron transporting materials as a host of phosphorescent compounds, doped with a novel iridium complex.

  Orthometalated complexes in which the central metal is platinum instead of iridium are also attracting attention. With respect to this type of complex, many examples are known in which ligands are characterized.

  In either case, the light emission brightness and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. There was a problem that it was lower than the conventional element.

  As described above, it is difficult for phosphorescent highly efficient light-emitting materials to shorten the light emission wavelength and improve the light emission lifetime of the device, and the performance that can withstand practical use cannot be sufficiently achieved.

  In addition, regarding wavelength shortening, introduction of an electron withdrawing group such as a fluorine atom, a trifluoromethyl group, a cyano group or the like into phenylpyridine as a substituent, and picolinic acid or a pyrazabole-based ligand as a ligand. It is known to introduce.

  However, with these ligands, the emission wavelength of the light-emitting material is shortened to achieve blue, and a high-efficiency device can be achieved. On the other hand, the light-emitting lifetime of the device is greatly deteriorated, so an improvement in the trade-off is required. It was.

  It has been disclosed that a metal complex having phenyltriazole as a ligand is a light-emitting material having a short emission wavelength (see, for example, Patent Document 1 and Non-Patent Document 1). Furthermore, metal complexes formed from similar phenyltriazole ligands are disclosed (for example, see Patent Documents 2, 3, and 4).

  However, in these patent documents and non-patent documents, from the viewpoint of coexistence of the emission wavelength and the emission lifetime of the device, there are still problems to be solved in the present situation where further shortening and longer lifetime are required. .

International Publication No. 2004/101707 International Publication No. 2005/123873 International Publication No. 2006/121811 US Patent Application Publication No. 2006/0251923

Chemistry of Materials, 18 (21), 5119-5129 (2006).

  An object of the present invention is to provide an organic EL element using an organic EL material that exhibits short-wave emission, exhibits high emission efficiency, and has a long emission lifetime, and further includes a display device including the element. And providing a lighting device.

  In particular, as an organic EL element material, it is to provide an organic EL element material that has a short phosphorescence lifetime of a light-emitting material, high light emission efficiency with blue to blue-green short-wave light emission, and a long light emission lifetime. .

  The above object of the present invention has been achieved by the following constitution.

1. In an organic electroluminescence device comprising a plurality of layers including at least one light emitting layer sandwiched between an anode and a cathode,
At least 1 layer of this light emitting layer has an organic layer containing at least 1 compound represented by following General formula (1), The organic electroluminescent element characterized by the above-mentioned.

[Wherein, ring A represents a triazole ring, and B ₁ and B ₂ each represent a carbon atom or a nitrogen atom. R ₁ represents a substituent, and l represents an integer of 0 or 1. R ₂ represents a substituent. R ₃ represents a hydrogen atom or a substituent, and n represents an integer of 0 or 1. R ₄ represents a substituent, and m represents an integer of 1 to 4. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ]
2. 2. The organic electroluminescence device according to 1 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[Wherein R ₁ and R ₂ each represent a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ]
3. 2. The organic electroluminescence device according to 1 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

[Wherein R ₂ represents a substituent. R ₃ represents a hydrogen atom or a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ]
4). At least one of R _{1 to} R ₄ of the general formula (1) described in 1 above, at least one of R ₁ , R ₂ and R ₄ of the general formula (2) described in 2 above or 3 above The organic according to any one of 1 to 3 above, wherein at least one of R ₂ , R ₃ and R _{4 in} the general formula (3) is a group represented by the following general formula (4): Electroluminescence element.

[In the formula, Z represents a 6-membered aromatic hydrocarbon group, a 6-membered aromatic heterocyclic group, a 5-membered aromatic heterocyclic group or a 5-membered heterocyclic group, and B represents a nitrogen atom or a carbon atom. To express. Ra represents a substituent having a steric parameter value (Es value) of -0.5 or less. Rb represents a hydrogen atom or a substituent, and n represents an integer of 1 to 4. * Indicates a bonding position. ]
5). 5. The organic electroluminescence device according to 4 above, wherein the group represented by the general formula (4) is a group represented by the following general formula (5).

[In the formula, Ra and Rb represent a group having the same meaning as Ra and Rb in the general formula (4), and n represents an integer having the same meaning as n in the general formula (4). * Indicates a bonding position. ]
6). 6. The organic electroluminescence device as described in 5 above, wherein the group represented by the general formula (5) is a group represented by the following general formula (6).

[In the formula, Ra and Rb represent the same groups as Ra and Rb in the general formula (4), and Rc represents a substituent having a steric parameter value (Es value) of −0.5 or less. n represents an integer of 1 to 3. * Indicates a bonding position. ]
7). The compound represented by the general formula (2) is a compound represented by the following general formula (7), wherein the organic electroluminescence device according to any one of 2 or 4 to 6 above.

[Wherein R ₂ represents a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. R ₅ and R ₆ each represent a substituent having a steric parameter value (Es value) of −0.5 or less. R ₇ represents a hydrogen atom or a substituent, and p represents an integer of 1 to 3. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ]
8). The compound represented by the general formula (3) is a compound represented by the following general formula (8), The organic electroluminescent element according to any one of the above 3 or 4-6.

[Wherein R ₃ represents a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. R ₅ and R ₆ each represent a substituent having a steric parameter value (Es value) of −0.5 or less. R ₇ represents a hydrogen atom or a substituent, and p represents an integer of 1 to 3. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ]
9. As a constituent layer, the compound represented by the general formula (1) described in 1 above, the compound represented by the general formula (2) described in 2 above, and the general formula (3) described in 3 above are used. A compound represented by the general formula (7) described in 7 above or an organic layer containing at least one compound represented by the general formula (8) described in 8 above, 9. The organic electroluminescence element according to any one of 1 to 8 above, which is formed using a wet process.

  10. 10. The organic electroluminescence element according to any one of 1 to 9, wherein M is platinum or iridium.

  11. The compound represented by the general formula (1) described in 1 above, the compound represented by the general formula (2) described in 2 above, the compound represented by the general formula (3) described in 3 above, the 7 An organic electroluminescent device material comprising at least one of the compound represented by the general formula (7) described in 8 or the compound represented by the general formula (8) described in 8 above.

  12 11. A display device comprising the organic electroluminescence element according to any one of 1 to 10 above.

  13. 11. An illumination device comprising the organic electroluminescence element according to any one of 1 to 10 above.

  According to the present invention, an organic EL element material useful for an organic EL element can be obtained. By using the element material, specific short-wave light emission can be seen, high emission efficiency, and a long emission lifetime can be obtained. An element, and a lighting device and a display device using the element can be provided.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

  In the organic electroluminescent element of this invention, the structure prescribed | regulated in any one of Claims 1-10 WHEREIN: The organic electroluminescent element which shows high luminous efficiency and has a long light emission lifetime, and illumination using this element A device and a display device could be provided.

  Moreover, the organic EL element material useful for the element could be molecularly designed.

  Hereinafter, details of each component according to the present invention will be sequentially described.

《Metal complex (also called metal complex compound)》
The metal complex (also referred to as a metal complex compound) according to the present invention will be described.

  The present inventors paid attention to the organic EL element material used for the light emitting layer of the organic EL element, and examined various metal complex compounds used as a light emitting dopant.

  In conventionally known metal complex compounds having a skeleton such as phenylpyrazole, short-wave luminescence is observed, but so-called non-radiation deactivation in which the luminescence is very weak or not observed at room temperature exhibits luminescence. Many cases were ruled.

  Among them, the present inventors proceeded with studies by molecular orbital calculation from the viewpoint of wavelength control and light emission improvement, and the metal complex compound containing a ligand skeleton having a specific structure emits short-wave light. And found to exhibit very high luminescent properties.

  Furthermore, in the synthesis of these compounds, it was found that the ligand structure was greatly stabilized by the substituent at a specific position, and it was possible to synthesize a metal complex compound that could hardly be obtained by conventional methods, and the present invention was completed.

  The present inventors have further studied and as shown in the compound (metal complex) represented by the general formula (1), (2), (3), (7) or (8) according to the present invention. When a simple skeleton was introduced, the light emitting wavelength shift of the light emitting material was small, and a light emitting dopant that realized a long lifetime at a desired light emitting wavelength was successfully developed.

  Here, the “skeleton” means a structure in which the transition metal element M and the ligand L are excluded from the compound represented by the general formula (1), (2), (3), (7) or (8). Means part. The skeleton itself is a ligand capable of coordinating with the transition metal element.

  Moreover, even if it is a ligand which has a mother nucleus based on this invention, the light emission wavelength of a metal complex is made into a desired area | region by introduce | transducing as a substituent the auxiliary | assistant ligand to combine and a substituent itself long wave. Can be controlled.

  Therefore, the inventor has designed the molecular design for imparting the function of controlling the emission wavelength of the metal complex in a long wave region (green to red) according to the general formulas (1), (2), (3 ), A partial structure obtained by removing the metal M and ligand L portions from the compound (metal complex compound) represented by (7) or (8) was used as a starting point for the basic skeleton design of the metal complex.

  The compound (metal complex) represented by the general formula (1), (2), (3), (7) or (8) according to the present invention has a valence of a transition metal element represented by M, Although it can have a plurality of ligands, the ligands may all be the same, or may have ligands having different structures.

  However, from the viewpoint of preferably obtaining the effects described in the present invention, the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type.

  The metal complex according to the present invention includes a ligand represented by the general formula (1), (2), (3), (7), or (8), as a ligand of the transition metal element M. A compound using only the above skeleton as a ligand without using L is most preferably used.

  Here, the ligand is a compound represented by the general formula (1), (2), (3), (7), or (8), which is coordinated to the transition metal element M. The partial structure represented (in the above general formula, each is defined as a ligand L), and the “skeleton” portion in each general formula is a ligand.

  Further, conventionally known ligands that can be used for forming the metal complex according to the present invention will be described in detail later.

  Of the compounds having a partial structure represented by the general formula (1) (metal complex), the compounds represented by the general formula (7) or (8) (metal complex) are particularly preferable compounds.

Furthermore, the substituents R ₁ to R ₄ of the compound (metal complex) having the partial structure represented by the general formula (1) and the compound (metal complex) represented by the general formula (2) or (3) At least one of them is preferably a group represented by the general formula (4), more preferably a group represented by the general formula (5), and particularly preferably a group represented by the general formula (6). ).

  The structure of the compound (metal complex) represented by the general formula (1), (2), (3), (7) or (8) according to the present invention will be described in detail later.

  By using such a metal complex as an organic EL element material, it was possible to provide an organic EL element, a lighting device, and a display device that exhibit high luminous efficiency and have a long emission lifetime.

(Charge transport layer)
The charge transport layer according to the present invention will be described.

  Furthermore, as a containing layer of the compound (metal complex) represented by the general formula (1), (2), (3), (7) or (8) according to the present invention, a charge transporting layer (charge) The transport layer is not particularly limited, and the charge transport layer is provided on the anode side with respect to the light emitting layer (referred to as a first charge transport layer), and is provided on the cathode side with respect to the light emitting layer ( Either embodiment of the second charge transport layer) may be employed.

  When the charge transport layer is provided on the anode side of the light emitting layer (also referred to as a first charge transport layer), the charge transport layer is preferably an electron blocking layer or a light emitting layer, and the charge transport layer is more than the light emitting layer. When provided on the cathode side (also referred to as the second charge transport layer), the charge transport layer is preferably a light emitting layer or a hole blocking layer, and more preferably, the charge transport layer is a light emitting layer or a hole blocking layer. The light emitting layer is particularly preferable.

  When contained in the light emitting layer, it can be used as a light emitting dopant in the light emitting layer to increase the efficiency of the external extraction quantum efficiency of the organic EL device of the present invention (higher brightness) and increase the light emission lifetime. it can.

  The constituent layers of the organic EL element of the present invention will be described in detail later.

(Group 8-10 transition metal elements in the periodic table represented by M)
Moreover, as a metal used for formation of the compound (metal complex) represented by the general formula (1), (2), (3), (7) or (8) according to the present invention, A transition metal element of group 8 to 10 (also simply referred to as a transition metal) is used, and among these, iridium and platinum are preferable transition metal elements.

  Hereinafter, the compound (metal complex) represented by the general formula (1), (2), (3), (7) or (8) according to the present invention will be described.

<< Compound Represented by Formula (1) (Metal Complex) >>
The compound represented by the general formula (1) according to the present invention will be described.

  First, the ring A will be described.

In the compound represented by the general formula (1), ring A represents a triazole ring, and B ₁ and B ₂ represent a carbon atom or a nitrogen atom. However, when _{B 1} is a nitrogen atom, _{B 2} represents a carbon atom, when _{B 2} is a nitrogen atom, _{B 1} represents a carbon atom.

In the compound represented by the general formula (1), the substituent represented by R ₁ is an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl) Group, propargyl group, etc.), aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group , Azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl Group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4- Triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl Group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) ), Quinoxalinyl group, pyridazinyl group, Azinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, Hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, Methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group) Group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl) Group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylamino) Sulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethyl Bonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy) Group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propyl) Carbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, Silcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group) Octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentyl) Ureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido ), Sulfinyl groups (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), An alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthyl) Sulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentyl) Ruamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg. , Fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group) Group, phenyldiethylsilyl group, etc.). These substituents may be further substituted with the above substituents. A plurality of these substituents may be bonded to each other to form a ring.

In the compound represented by the general formula (1), l represents an integer of 0 or 1. That is, when B ₂ in the general formula (1) is a nitrogen atom, l is 0 or 1, and 1 is 1 when B ₂ in the general formula (1) is a carbon atom.

In the compound represented by the general formula (1), the substituent represented by R ₂ has the same meaning as R ₁ in the general formula (1).

In the compound represented by the general formula (1), R ₃ represents a hydrogen atom or a substituent, and the substituent represented by R ₂ has the same meaning as R ₁ in the general formula (1).

In the compound represented by the general formula (1), n represents an integer of 0 or 1. That is, n is 0 when B ₁ in the general formula (1) is a nitrogen atom, and n is ₁ when B ₁ in the general formula (1) is a carbon atom.

In the compound represented by the general formula (1), R ₃ represents a hydrogen atom or a substituent, and the substituent represented by R ₃ has the same meaning as R ₁ in the general formula (1).

In the compound represented by the general formula (1), R ₄ represents a hydrogen atom or a substituent, and the substituent represented by R ₄ has the same meaning as R ₁ in the general formula (1).

In the compound represented by the general formula (1), m represents an integer of 1 to 4. Each R ₄ may be the same or different. Further, when a plurality of R ₄ are present, they may be bonded to each other to form a ring.

  In the compound represented by the general formula (1), (2), (3), (7) or (8), L represents an arbitrary ligand capable of coordinating with M. It is a rank. There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Published by Yersin in 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabo Company, Akio Yamamoto, published in 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands). Furthermore, substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, picolinic acid, carbene and the like can be used in combination as a preferred ligand.

  In the compound represented by the general formula (1), (2), (3), (7) or (8), m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2.

<< Compound Represented by Formula (2) >>
In the compound represented by the general formula (2), the substituent represented by R ₁ , R ₂ and R ₄ has the same meaning as the substituent described in the compound represented by the general formula (1). Each of the substituents may further have the aforementioned substituent. m, L, m1, and m2 are synonymous with m, L, m1, and m2 described in the compound represented by the general formula (1).

<< Compound Represented by Formula (3) >>
In the compound represented by the general formula (3), the substituent represented by R ₂ , R ₃ and R ₄ has the same meaning as the substituent described in the compound represented by the general formula (1). . Each of the substituents may further have the aforementioned substituent. m, L, m1, and m2 are synonymous with m, L, m1, and m2 described in the compound represented by the general formula (1).

<< Preferred Aspect of Substituent of General Formula (1), (2) or (3) >>
In the compound represented by the general formula (1), (2) or (3), at least one of the substituents R ₁ to R ₄ is preferably a group represented by the following general formula (4), More preferred is a group represented by the following general formula (5), and particularly preferred is a group represented by the following general formula (6).

  Hereinafter, groups represented by the general formulas (4) to (6) will be described.

<< Group Represented by General Formula (4) >>
In the general formula (4), Z represents a 6-membered aromatic hydrocarbon group, a 6-membered aromatic heterocyclic group, a 5-membered aromatic heterocyclic group or a 5-membered heterocyclic group, and B represents a nitrogen atom or Represents a carbon atom.

  In the general formula (4), examples of the 6-membered aromatic hydrocarbon ring represented by Z include a benzene ring. Furthermore, you may have the substituent mentioned later.

  In the general formula (4), examples of the 6-membered aromatic heterocycle represented by Z include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring.

  In the general formula (4), examples of the 5-membered heterocyclic ring represented by Z include dihydrothiophene, tetrahydrothiophene, pyrrolidone, dihydropyrrole, tetrahydrofuran, dihydrofuran, dihydrophosphole, phosphorane, silolane, dihydrosilole, dihydro Examples include imidazole, dihydropyrazole, dihydrooxazole, dihydrothiazole, dihydroisooxazole, dihydroisothiazole and the like.

  In the general formula (4), examples of the 5-membered aromatic heterocycle represented by Z include thiophene, pyrrole, furan, phosphole, silole, imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, isothiazole, And oxazole.

In the general formula (4), the substituent represented by Rb has the same meaning as the substituent represented by R ₁ in the compound represented by the general formula (1).

  In the general formula (4), a substituent having a steric parameter value (Es value) represented by Ra of −0.5 or less will be described in detail below. Further, the substituent constitutes a 6-membered aromatic hydrocarbon group, a 6-membered aromatic heterocyclic group, a 5-membered aromatic heterocyclic group or a 5-membered heterocyclic group formed by the Z. It is preferably bonded to an atom adjacent to A, and more preferably, it is also an electron donating group which will be described in detail below.

  Hereinafter, the three-dimensional parameter value (Es value) will be described.

(3D parameter value (Es value))
In the present invention, the Es value is a steric parameter derived from chemical reactivity. The smaller this value, the more sterically bulky substituent can be said.

  In general, in ester hydrolysis under acidic conditions, it is known that the influence of substituents on the progress of the reaction may only be considered as steric hindrance. The Es value is obtained by quantifying the steric hindrance.

The Es value of the substituent X is represented by the following chemical reaction formula: X—CH ₂ COORX + H ₂ O → X—CH ₂ COOH + RXOH
The reaction rate constant kX for hydrolyzing an α-monosubstituted acetic acid ester derived from α-monosubstituted acetic acid in which one hydrogen atom of the methyl group of acetic acid is substituted with the substituent X represented by the formula And the following chemical reaction formula CH ₃ COORY + H ₂ O → CH ₃ COOH + RYOH
(RX is the same as RY), which is obtained from the reaction rate constant kH when the acetate corresponding to the α-monosubstituted acetate described above is hydrolyzed under acidic conditions.

Es = log (kX / kH)
The reaction rate decreases due to the steric hindrance of the substituent X, and as a result, kX <kH, so the Es value is usually negative. When the Es value is actually obtained, the above two reaction rate constants kX and kH are obtained and calculated by the above formula.

  Specific examples of Es values are given by Unger, S. et al. H. Hansch, C .; , Prog. Phys. Org. Chem. 12, 91 (1976). The specific numerical values are also described in “Structure-activity relationship of drugs” (Regional Chemistry Special Issue 122, Nankodo) and “American Chemical Society Reference Book, 'Exploring QSAR' p.81 Table 3-3”. There is. Next, a part is shown in Table 1.

  Here, it should be noted that the Es value as defined in this specification is not defined by defining that of a methyl group as 0, but by assuming that a hydrogen atom is 0, and an Es value where a methyl group is 0. Minus 1.24.

  The Es value according to the present invention is −0.5 or less. Preferably it is -7.0--0.6. Most preferably, it is -7.0 to -1.0.

  Here, in the present invention, when a steric parameter value (Es value) is -0.5 or less, for example, a keto-enol tautomer may exist in Z, the keto moiety is regarded as an enol isomer. Es value is converted. Even when other tautomerism exists, the Es value is converted by the same conversion method. Furthermore, the substituent having an Es value of −0.5 or less is preferably an electron-donating substituent in terms of electronic effect.

(Electron donating group (electron donating substituent))
In the present invention, the electron-donating substituent is a substituent having a negative Hammett σp value as described below, and such a substituent has an electron on the bonding atom side compared to a hydrogen atom. Easy to give.

  Specific examples of the substituent exhibiting electron donating properties include a hydroxy group, a mercapto group (also referred to as a thiol group), an alkoxy group (for example, a methoxy group), an alkylthio group, an arylthio group, an acetyloxy group, an amino group, and a dimethylamino group. , An acetylamino group, an alkyl group (for example, methyl group, ethyl group, propyl group, t-butyl group) and an aryl group (for example, phenyl group, mesityl group, etc.). For the Hammett σp value, for example, the following documents can be referred to.

  The Hammett σp value according to the present invention refers to Hammett's substituent constant σp. Hammett's σp value is a substituent constant determined by Hammett et al. From the electronic effect of the substituent on the hydrolysis of ethyl benzoate. The groups described in “Constants for Correlation Analysis in Chemistry and Biology” (C. Hansch and A. Leo, John Wiley & Sons, New York, 1979) can be cited.

  In the present invention, the group represented by the general formula (5) or the general formula (6) is preferable among the groups represented by the general formula (4).

<< Group Represented by General Formula (5) >>
In the general formula (5), the substituent represented by Ra having a steric parameter value (Es value) of −0.5 or less is the steric parameter value (Es value) represented by Ra in the general formula (4). Is synonymous with a substituent of -0.5 or less.

In the general formula (5), the substituent represented by Rb has the same meaning as the substituent represented by R ₁ in the partial structure represented by the general formula (1).

<< Group Represented by General Formula (6) >>
In the general formula (6), the substituents each represented by Ra and Rc and having a steric parameter value (Es value) of −0.5 or less are the steric parameter values represented by Ra in the general formula (4) ( (Es value) is synonymous with a substituent of -0.5 or less.

In the general formula (6), the substituent represented by Rb has the same meaning as the substituent represented by R ₁ in the partial structure represented by the general formula (1).

  Moreover, in this invention, the compound represented by either the said general formula (7) or (8) among the compounds represented by the said general formula (1), (2) or (3) is preferable.

<< Compound Represented by Formula (7) >>
The compound represented by the general formula (7) according to the present invention will be described.

In the compound represented by the general formula (7), the substituent represented by R ₂ and R ₄ has the same meaning as the substituent represented by R ₁ in the compound represented by the general formula (1). . Each of the substituents may further have the aforementioned substituent.

In the compound represented by the general formula (7), R ₂ is preferably an alkyl group or an aryl group.

In the compound represented by the general formula (7), R ₅ and R ₆ represent a substituent having a steric parameter value (Es value) of −0.5 or less, and have the same meaning as the description of Ra in the general formula (4). .

In the compound represented by the general formula (7), R ₇ represents a hydrogen atom or a substituent, and the substituent represented by R ₇ has the same meaning as the substituent represented by R ₁ in the general formula (1). It is.

  In the compound represented by the general formula (7), p represents an integer of 1 to 3.

  In the compound represented by the general formula (7), m, L, m1 and m2 have the same meanings as m, L, m1 and m2 described in the compound represented by the general formula (1).

<< Compound Represented by Formula (8) >>
The compound represented by the general formula (8) according to the present invention will be described.

In the compound represented by the general formula (8), the substituent represented by R ₃ and R ₄ has the same meaning as the substituent represented by R ₁ in the compound represented by the general formula (1). . Each of the substituents may further have the aforementioned substituent.

In the compound represented by the general formula (8), R ₃ is preferably an alkyl group or an aryl group, preferably an alkyl group.

In the compound represented by the general formula (8), R ₅ and R ₆ represent a substituent having a steric parameter value (Es value) of −0.5 or less, and have the same meaning as the description of Ra in the general formula (4). .

In the compound represented by the general formula (8), R ₇ represents a hydrogen atom or a substituent, and the substituent represented by R ₇ has the same meaning as the substituent represented by R ₁ in the general formula (1). It is.

  In the compound represented by the general formula (8), p represents an integer of 1 to 3.

  In the compound represented by the general formula (8), m, L, m1 and m2 have the same meanings as m, L, m1 and m2 described in the compound represented by the general formula (1).

(Ligand applicable to formation of metal complex according to the present invention)
In forming the metal complex (metal complex compound) according to the present invention, a conventionally known ligand described later can be used in combination as necessary. Moreover, as what is called a ligand, the said trader can use together a well-known ligand (it is also called a coordination compound) as a ligand as needed.

  There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Published by Yersin in 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabo Company, Akio Yamamoto, published in 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands).

  Hereinafter, the compound represented by any one of the general formulas (1), (2), (3), (7), (8) or (9) according to the present invention (also referred to as a metal complex or a metal complex compound). Although the specific example of this is shown, this invention is not limited to these.

  Although the synthesis example of exemplary compound 1-15 as described in said specific example is shown below, this invention is not limited to these.

<< Synthesis Example: Synthesis of Exemplary Compound 1-15 >>
4-methyl-3-methyl-5-phenyl-4H-1,2,4-triazole 2 g (0.007211 mol) and tris (acetylacetonato) iridium (III) 0.5 g (0.001021 mol) were nitrogenated. After replacement, the reaction vessel was sealed and heated in a mantle heater at 240 ° C. to 280 ° C. for 5 minutes, and then the resulting crude product was separated by column chromatography (THF-Toluene) to give Exemplified Compound 1-15 as 1 Obtained .05 g (84%).

  In addition, the above metal complexes are described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), Organic Letter, vol. 3, pp. 415-418 (2006).

  In the present invention, the emission wavelength of the exemplified compound was measured as follows. First, an absorption spectrum of the exemplary compound is measured, and an absorption maximum wavelength in the range of 300 nm to 350 nm is set as excitation light.

  Using the set excitation light, the emission wavelength is measured with a fluorometer F-4500 (manufactured by Hitachi, Ltd.) while performing nitrogen bubbling.

  In addition, although there is no restriction | limiting in the solvent which can be used, 2-methyltetrahydrofuran, a dichloromethane, etc. are used preferably from a soluble viewpoint of a compound.

The concentration at the time of measurement is preferably sufficiently diluted, and specifically, it is preferably measured in the range of 10 ⁻⁶ mol / l to 10 ⁻⁴ mol / l.

  Moreover, there is no restriction | limiting in particular as temperature at the time of measurement, However, Generally, it is preferable that temperature setting of the range of room temperature-77K is performed.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) Anode / hole transport layer / electron block layer / light emitting layer / hole block layer / electron transport layer / cathode In the organic EL device of the present invention, blue light emission The light emission maximum wavelength of the layer is preferably in the range of 430 nm to 480 nm, the green light emission layer is preferably a monochromatic light emitting layer having a light emission maximum wavelength in the range of 510 nm to 550 nm, and the red light emission layer is in the range of light emission maximum wavelength of 600 nm to 640 nm. This is a display device using these. It is preferred.

  Alternatively, a white light emitting layer may be formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention is preferably an organic EL element having a white light emitting layer, and is preferably a lighting device using these.

  Each layer which comprises the organic EL element of this invention is demonstrated.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 nm to 200 nm, and particularly preferably in the range of 10 nm to 20 nm.

  For the production of the light-emitting layer, a light-emitting dopant or a host compound, which will be described later, is formed by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink-jet method. it can.

  The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and at least one kind of light emitting dopant (such as a phosphorescent dopant (also referred to as a phosphorescent dopant) or a fluorescent dopant).

(Host compound (also called luminescent host))
The host compound used in the present invention will be described.

  Here, the host compound in the present invention is a phosphorescent quantum yield of phosphorescence emission at a room temperature (25 ° C.) having a mass ratio of 20% or more in the compound contained in the light emitting layer. Is defined as a compound of less than 0.1. The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

  The light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). A light emitting host), or one or more compounds such as the material C may be used.

  Although the specific example of the host compound preferably used for this invention below is shown, this invention is not limited to these.

  In addition, compounds in which a substituent such as an aryl group, a dibenzofuranyl group, a carbazolyl group, or the like, or a compound in which the dibenzofuranyl group is replaced with a dibenzothiophenyl group are also preferably used. Furthermore, a polymer having a polymerizable group as a substituent or a compound composed of these compounds is also preferably used.

  Of these host compounds, compounds having a molecular weight of 500 to 2000 are preferably used. In the case of a polymer, a polymer having an average molecular weight of 20,000 to 1,000,000 is preferably used.

  As a known host compound that may be used in combination, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.

  Specific examples of known host compounds include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(Luminescent dopant)
The light emitting dopant according to the present invention will be described.

  As the light-emitting dopant according to the present invention, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used. From the viewpoint of obtaining an organic EL device with high luminous efficiency, the light emitting dopant used in the light emitting layer or the light emitting unit of the organic EL device of the present invention (sometimes simply referred to as a light emitting material) contains the above host compound. At the same time, it is preferable to contain a phosphorescent dopant.

  The compound represented by any one of the general formulas (1), (2), (3), (7) or (8) according to the present invention (also referred to as a metal complex or a metal complex compound) In the constituent layer of the organic EL element of the invention, it is particularly preferably used in the light emitting layer, and in the light emitting layer, it is preferably used as a light emitting dopant, and more preferably used as a phosphorescent dopant.

(Phosphorescent dopant)
The phosphorescent dopant according to the present invention will be described.

  The phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.) and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.

  There are two types of light emission of phosphorescent dopants in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant. The energy transfer type that obtains light emission from the phosphorescent dopant, and the other is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. Although it is a trap type, in any case, the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.

  The phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device.

  The phosphorescent dopant is preferably a complex compound containing a group 8-10 metal in the periodic table, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex. Of these, iridium compounds are most preferred.

  Moreover, as a compound which can be used together with the compound represented by any one of the general formulas (1), (2), (3), (7) or (8) according to the present invention, the following patents Examples include compounds described in the publication.

  International Publication No. 00/70655, JP 2002-280178, JP 2001-181616, JP 2002-280179, JP 2001-181617, JP 2002-280180, JP JP 2001-247859, JP 2002-299060, JP 2001-313178, JP 2002-302671, JP 2001-345183, JP 2002-324679, International Publication No. 02. No./15645, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-117978 A. Gazette, JP 2002-338588 A JP 2002-170684 A, JP 2002-352960 A, WO 01/93642, JP 2002-50483, JP 2002-1000047, JP 2002-173684 A, JP JP 2002-359082 A, JP 2002-175484 A, JP 2002-363552 A, JP 2002-184582 A, JP 2003-7469 A, JP 2002-525808 A, JP 2003-2003 A. 7471, JP-A 2002-525833, JP-A 2003-31366, JP-A 2002-226495, JP-A 2002-234894, JP-A 2002-235076, JP-A 2002-241751 Publication, Unexamined-Japanese-Patent No. 2001-319779, Open 2001-319780, JP 2002-62824, JP 2002-100474, JP 2002-203679, JP 2002-343572, JP-2002-203678 Patent Publication JP.

  Some specific examples are shown below.

(Fluorescent dopant (also called fluorescent compound))
Fluorescent dopants (fluorescent compounds) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes Examples thereof include dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Next, a charge transport layer used as a constituent layer of the organic EL device of the present invention, that is, an injection layer, a blocking layer, an electron transport layer, and the like will be described.

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.

  Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

  The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

  The hole blocking layer contains the carbazole derivative, carboline derivative, diazacarbazole derivative (one in which one of the carbon atoms constituting the carboline ring of the carboline derivative is replaced with a nitrogen atom) mentioned as the host compound. It is preferable to do.

  In the present invention, when a plurality of light emitting layers having different light emission colors are provided, the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode. Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

  The ionization potential is defined by the energy required to emit an electron at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.

  (1) Keywords using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), which is molecular orbital calculation software manufactured by Gaussian, USA. The ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

  (2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

  In addition, it is also possible to contain the compound represented by any one of the general formulas (1), (2), (3), (7) or (8) according to the present invention in the hole blocking layer. .

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.

  Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.

  The compound represented by any one of the general formulas (1), (2), (3), (7) or (8) according to the present invention may be contained in the electron blocking layer.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.

  Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.

  Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use an electron transport layer having such a high n property because an element with lower power consumption can be manufactured.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the said metal by the film thickness of 1 nm-20 nm to a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc., and it is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 ⁻³ ml / (m ² · 24 h · MPa) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.

  Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

  In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned.

Furthermore, the polymer film has a oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · MPa) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can. Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials.

  The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

  In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

  In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.

  Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

  The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.

  This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.

  However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.

  At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

  The arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL element of the present invention is processed on the light extraction side of the substrate, for example, so as to provide a microlens array-like structure, or in combination with a so-called condensing sheet, for example, with respect to a specific direction, for example, the element light emitting surface. By condensing in the front direction, the luminance in a specific direction can be increased.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm, to form an anode.

  Next, organic compound thin films such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, are formed thereon.

  As a method for forming each of these layers, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above, but it is easy to obtain a uniform film and pinholes are not easily generated. In view of the above, film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.

  Examples of the liquid medium for dissolving or dispersing the organic EL material include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, mesitylene, cyclohexylbenzene and the like. Aromatic hydrocarbons, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  After these layers are formed, a thin film made of a cathode material is formed thereon by 1 μm or less, preferably by a method such as vapor deposition or sputtering so that the film thickness is in the range of 50 nm to 200 nm. By providing, a desired organic EL element can be obtained.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the structure of the compound used in an Example is shown below.

  In the above, Compound A was synthesized as follows with reference to the method described in International Publication No. 2005/123873.

<< Synthesis of Compound A >>
3,4-dimethyl-5-phenyl-4H-1,2,4-triazole and tris (acetylacetonato) iridium (III) were purged with nitrogen and sealed, and in the same manner as the above exemplary compound 1-15 Synthesis was carried out, but only a trace amount of Compound A was obtained. As a result of analysis by NMR (Nuclear Magnetic Resonance) and MS (Mass Spectrometry), a decomposition product of 3,4-dimethyl-5-phenyl-4H-1,2,4-triazole was found. It was seen.

Example 1
<< Production of Organic EL Element 1-1 >>
A quartz substrate of 100 mm × 100 mm × 1.1 mm was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. This quartz substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of H-1 is placed as a host compound in a molybdenum resistance heating boat, and 100 mg of compound A is placed in another molybdenum resistance heating boat as a vacuum deposition. Attached to the device.

Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing H-1 and Compound B was energized and heated, and the deposition rates were 0.2 nm / second and 0.018 nm / second, respectively. A 40 nm-thick luminescent layer was provided by co-evaporation on the quartz substrate. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  On the light emitting surface of the quartz substrate after fabrication, an epoxy-based photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material using a 300 μm-thick sealing glass as a sealing substrate. Then, this was superimposed on the above quartz substrate, irradiated with UV light, cured, sealed, and an illumination device was produced and evaluated.

<< Production of Organic EL Elements 1-2 to 1-10 >>
In the production of the organic EL element 1-1, organic EL elements 1-2 to 1-10 were respectively produced in the same manner except that the compound B as the dopant was changed to the compounds shown in Table 2.

<< Measurement of PL relative quantum yield >>
About each of the obtained organic EL elements 1-1 to 1-10, the dopant was excited by irradiation with excitation light, and the peak area value of the obtained emission spectrum was obtained. This area value is a value obtained by correcting absorption by excitation light. The measurement was performed with Hitachi spectrophotometer U-3300 and fluorophotometer F-4500.

  The organic EL elements 1-2 to 1-10 were evaluated by setting the peak area obtained with the organic EL element 1-1 (compound B) to 1.

  The obtained results are shown in Table 2.

  From Table 2, it can be seen that the organic EL element of the present invention has a higher PL quantum yield and quenching due to the concentration than the comparative organic EL element.

Example 2
<< Preparation of Organic EL Element 2-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was put in a molybdenum resistance heating boat, and 200 mg of H-1 as a host compound was put in another molybdenum resistance heating boat, 200 mg of BAlq is put into another molybdenum resistance heating boat, 100 mg of FIrpic (Ir-12) is put into another resistance heating boat made of molybdenum, and 200 mg of Alq ₃ is put into another resistance heating boat made of molybdenum. Installed.

Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was heated by heating, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. The hole transport layer was provided.

  Further, the heating boat containing H-1 and FIrpic (Ir-12) is energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively. Thus, a light emitting layer having a thickness of 40 nm was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Further, the heating boat containing BAlq was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.

In addition, the heating boat containing Alq ₃ is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Subsequently, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited to form a cathode, and an organic EL element 2-1 was produced.

  The non-light-emitting surface of each organic EL element after fabrication is covered with a glass case, a 300 μm thick glass substrate is used as a sealing substrate, and an epoxy photo-curing adhesive (LUX Track LC0629B) is applied, stacked on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, as shown in FIGS. Such a lighting device was formed and evaluated.

  FIG. 3 shows a schematic diagram of the lighting device, in which the organic EL element 101 is covered with a glass cover 102 (note that the sealing operation with the glass cover is performed without bringing the organic EL element 101 into contact with the atmosphere. (It was performed in a glove box under an atmosphere (under an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more)).

  4 shows a cross-sectional view of the lighting device. In FIG. 2, 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

<< Production of Organic EL Elements 2-2 to 2-30 >>
In the production of the organic EL element 2-1, organic EL elements 2-2 to 2-30 were produced in the same manner except that the host compound and the dopant compound were changed as shown in Table 3.

<< Evaluation of Organic EL Elements 2-1 to 2-30 >>
The organic EL elements 2-1 to 2-30 produced as follows were evaluated and the results are shown in Table 3.

(Luminescent efficiency (also called external extraction quantum efficiency))
About the produced organic EL element, external extraction quantum efficiency (%) when ^2.5 mA / cm ² constant current was applied in a dry nitrogen gas atmosphere at 23 ° C. was measured. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used in the same manner.

  The measurement results of the external extraction quantum efficiency in Table 2 were expressed as relative values when the measured value of the organic EL element 2-1 was 100.

(Half life)
The half-life was evaluated according to the measurement method shown below.

Each organic EL device driven with a constant current at a current giving an initial luminance 1000 cd / ^{m 2,} obtains the time to be 1/2 (500cd / ^{m 2)} of the initial luminance, which was used as a measure of the half-life. The half life was expressed as a relative value when the comparative organic EL element 2-1 was set to 100.

(Initial deterioration)
The initial deterioration was evaluated according to the measurement method shown below. When the half-life was measured, the time required for the luminance to reach 90% was measured and used as a measure of initial deterioration. The initial deterioration was 100 for the comparative organic EL element 2-1. The initial deterioration was calculated based on the following formula.

Initial deterioration = (luminance 90% arrival time of organic EL element 2-1) / (luminance 90% arrival time of each element) × 100
That is, the smaller the initial deterioration value, the smaller the initial deterioration.

(Dark spot)
The light emitting surface when each organic EL element was continuously lit under a constant current condition of ^2.5 mA / cm ² at room temperature was visually evaluated. The following rank evaluation was performed by visual evaluation by 10 people extracted at random.

×: When the number of confirmed dark spots is 5 or more Δ: When the number of confirmed dark spots is 1 to 4 ○: When the number of confirmed dark spots is 0

  From Table 3, it is clear that the organic EL device of the present invention has higher luminous efficiency, longer half-life, less initial degradation, and less dark spots compared to the comparative organic device. is there.

Example 3
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL element 2-12 of Example 1 was used as a blue light emitting element.

(Production of green light emitting element)
A green light emitting device was produced in the same manner as in the organic EL device 2-1 of Example 1 except that FIrPic (Ir-12) was changed to Ir-1, and this was used as a green light emitting device.

(Production of red light emitting element)
A red light emitting device was produced in the same manner as in the organic EL device 2-1 of Example 1, except that FIrPic (Ir-12) was changed to Ir-9, and this was used as a red light emitting device.

  The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate to produce an active matrix type full-color display device having a configuration as shown in FIG. In FIG. 2, only the schematic diagram of the display part A of the produced display device is shown.

  That is, a plurality of pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate. The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions (for details, see FIG. Not shown).

  The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. The image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was produced by appropriately juxtaposing red, green, and blue pixels.

  It has been found that when this full-color display device is driven, a high-brightness, high durability, and clear full-color moving image display can be obtained.

Example 4
<< Preparation of white light emitting element and white lighting device >>
The electrode of the transparent electrode substrate of Example 1 was patterned to 20 mm × 20 mm, and α-NPD was formed thereon with a thickness of 25 nm as a hole injection / transport layer in the same manner as in Example 1; The heated boat containing 1 and the boat containing Compound 1-14 and the boat containing Ir-9 are energized independently, and H-1 as a light emitting host and Illustrative Compound 1-14 as a light emitting dopant, and The vapor deposition rate of Ir-9 was adjusted to 100: 5: 0.6, vapor deposition was performed to a thickness of 30 nm, and a light emitting layer was provided.

Next, 10 nm of BAlq was deposited to provide a hole blocking layer. Furthermore, it was deposited Alq ₃ at 40nm an electron transporting layer.

  Next, as in Example 2, a square perforated mask having the same shape as the transparent electrode made of stainless steel was placed on the electron injection layer, and lithium fluoride 0.5 nm was used as the cathode buffer layer and aluminum 150 nm was used as the cathode. Vapor deposition and film formation were performed.

  This element was provided with a sealing can having the same method and the same structure as in Example 2 to produce a flat lamp as shown in FIGS. When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 5
<< Production of White Light Emitting Element and White Lighting Device-2 >>
After patterning on a substrate (NH-Techno Glass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds. Then, the film was formed by spin coating and then dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound A dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to perform photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to obtain a second hole transport layer (electron blocking layer).

  Next, using a solution of H-5 (60 mg), Exemplified Compound 1-12 (3.0 mg) and Ir-9 (3.0 mg) dissolved in 6 ml of toluene, the spin coating method was performed at 1000 rpm for 30 seconds. To form a light emitting layer.

  Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200 mg of BAlq was put into a molybdenum resistance heating boat, and attached to the vacuum deposition apparatus.

The vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing the heating boat containing BAlq, and deposited on the light emitting layer at a deposition rate of 0.1 nm / sec. The electron transport layer was provided.

  In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the white light emitting organic EL element was produced.

  When this element was energized, almost white light was obtained, and it was found that it could be used as a lighting device. Furthermore, the same element was created using the exemplary compounds 1-16, 1-30, and 2-20 instead of the exemplary compound 1-12. In the case where the light emitting material has a polymerizable group, ultraviolet light was irradiated for 180 seconds to perform photopolymerization / crosslinking, and then vacuum dried at 60 ° C. for 1 hour to obtain a light emitting layer. When these elements were energized, almost white light was obtained, and it was found that they could be used as a lighting device.

Example 6
<< Preparation of white light emitting element and white illumination device-3 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds. After the film formation by spin coating, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound D dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.

  Next, by using a solution obtained by dissolving Compound E (60 mg), Ir-14 (3.0 mg), and Exemplified Compound 1-16 (3.0 mg) in 6 ml of toluene, the spin coating method was performed at 1000 rpm for 30 seconds. A film was formed. Irradiated with ultraviolet light for 15 seconds to cause photopolymerization / crosslinking, and further heated in vacuum at 150 ° C. for 1 hour to obtain a light emitting layer.

  Furthermore, a film in which compound F (20 mg) was dissolved in 6 ml of toluene was used to form a film by spin coating under conditions of 1000 rpm and 30 seconds. Ultraviolet light was irradiated for 15 seconds, photopolymerization / crosslinking was performed, and further heating was performed in vacuum at 80 ° C. for 1 hour to form a hole blocking layer.

Subsequently, this substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, 200 mg of Alq ₃ was placed in a molybdenum resistance heating boat, and attached to the vacuum vapor deposition apparatus. After depressurizing the vacuum chamber to 4 × 10 ⁻⁴ Pa, energizing and heating the heating boat containing Alq ₃ , depositing on the hole blocking layer at a deposition rate of 0.1 nm / second, An electron transport layer having a thickness of 40 nm was provided.

  In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the white light emitting organic EL element was produced.

  When this element was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line A Display part B Control part 101 Organic EL element 107 Glass substrate with a transparent electrode 106 Organic EL layer 105 Cathode 102 Glass cover 108 Nitrogen gas 109 Water catching agent

Claims (13)

In an organic electroluminescence device comprising a plurality of layers including at least one light emitting layer sandwiched between an anode and a cathode,
At least 1 layer of this light emitting layer has an organic layer containing at least 1 compound represented by following General formula (1), The organic electroluminescent element characterized by the above-mentioned.

[Wherein, ring A represents a triazole ring, and B ₁ and B ₂ each represent a carbon atom or a nitrogen atom. R ₁ represents a substituent, and l represents an integer of 0 or 1. R ₂ represents a substituent. R ₃ represents a hydrogen atom or a substituent, and n represents an integer of 0 or 1. R ₄ represents a substituent, and m represents an integer of 1 to 4. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[Wherein R ₁ and R ₂ each represent a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ] The organic electroluminescent device according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

[Wherein R ₂ represents a substituent. R ₃ represents a hydrogen atom or a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ] At least one of R _{1 to} R ₄ of the general formula (1) according to claim 1, at least one of R ₁ , R ₂ and R ₄ of the general formula (2) according to claim 2, or claim 3 _{4. At} least one of R ₂ , R _3, and R _{4 in} the general formula (3) according to claim 1 is a group represented by the following general formula (4). The organic electroluminescent element of description.

[In the formula, Z represents a 6-membered aromatic hydrocarbon group, a 6-membered aromatic heterocyclic group, a 5-membered aromatic heterocyclic group or a 5-membered heterocyclic group, and B represents a nitrogen atom or a carbon atom. To express. Ra represents a substituent having a steric parameter value (Es value) of -0.5 or less. Rb represents a hydrogen atom or a substituent, and n represents an integer of 1 to 4. * Indicates a bonding position. ] The organic electroluminescent device according to claim 4, wherein the group represented by the general formula (4) is a group represented by the following general formula (5).

[In the formula, Ra and Rb represent a group having the same meaning as Ra and Rb in the general formula (4), and n represents an integer having the same meaning as n in the general formula (4). * Indicates a bonding position. ] The organic electroluminescent device according to claim 5, wherein the group represented by the general formula (5) is a group represented by the following general formula (6).

[In the formula, Ra and Rb represent the same groups as Ra and Rb in the general formula (4), and Rc represents a substituent having a steric parameter value (Es value) of −0.5 or less. n represents an integer of 1 to 3. * Indicates a bonding position. ] The compound represented by the general formula (2) is a compound represented by the following general formula (7), The organic electroluminescence according to any one of claims 2 to 4-6 element.

[Wherein R ₂ represents a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. R ₅ and R ₆ each represent a substituent having a steric parameter value (Es value) of −0.5 or less. R ₇ represents a hydrogen atom or a substituent, and p represents an integer of 1 to 3. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ] 7. The organic electroluminescence according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (8). element.

[Wherein R ₃ represents a substituent. R ₄ represents a hydrogen atom or a substituent, and m represents an integer of 1 to 4. R ₅ and R ₆ each represent a substituent having a steric parameter value (Es value) of −0.5 or less. R ₇ represents a hydrogen atom or a substituent, and p represents an integer of 1 to 3. M represents a group 8-10 transition metal element in the periodic table, and L represents an arbitrary ligand capable of coordinating with M. m1 represents an integer of 1 to 3, and m2 represents an integer of 0 to 2. ]   As a constituent layer, a compound represented by the general formula (1) according to claim 1, a compound represented by the general formula (2) according to claim 2, and a general formula (3) according to claim 3. An organic layer containing at least one compound represented by general formula (7) according to claim 7, or a compound represented by general formula (8) according to claim 8. The organic electroluminescent device according to claim 1, wherein the organic layer is formed using a wet process.   The organic electroluminescence device according to any one of claims 1 to 9, wherein M is platinum or iridium.   A compound represented by the general formula (1) according to claim 1, a compound represented by the general formula (2) according to claim 2, and a compound represented by the general formula (3) according to claim 3. An organic electroluminescence device comprising at least one compound represented by the general formula (7) according to claim 7 or a compound represented by the general formula (8) according to claim 8 material.   A display device comprising the organic electroluminescence element according to claim 1.   The illuminating device provided with the organic electroluminescent element of any one of Claims 1-10.

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